WO2013005634A1 - アクリル系熱可塑性樹脂組成物及びその成形体 - Google Patents

アクリル系熱可塑性樹脂組成物及びその成形体 Download PDF

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WO2013005634A1
WO2013005634A1 PCT/JP2012/066550 JP2012066550W WO2013005634A1 WO 2013005634 A1 WO2013005634 A1 WO 2013005634A1 JP 2012066550 W JP2012066550 W JP 2012066550W WO 2013005634 A1 WO2013005634 A1 WO 2013005634A1
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group
carbon atoms
structural unit
acrylic
thermoplastic resin
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PCT/JP2012/066550
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English (en)
French (fr)
Japanese (ja)
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真実 米村
真由子 木村
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旭化成ケミカルズ株式会社
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Application filed by 旭化成ケミカルズ株式会社 filed Critical 旭化成ケミカルズ株式会社
Priority to IN2445MUN2013 priority Critical patent/IN2013MN02445A/en
Priority to JP2012549194A priority patent/JP5190564B2/ja
Priority to EP12807338.4A priority patent/EP2727961B8/en
Priority to CN201280030159.7A priority patent/CN103619946B/zh
Priority to KR1020137033322A priority patent/KR101536505B1/ko
Priority to US14/129,230 priority patent/US10030134B2/en
Publication of WO2013005634A1 publication Critical patent/WO2013005634A1/ja
Priority to US15/298,786 priority patent/US20170037236A1/en
Priority to US16/029,494 priority patent/US20180312682A1/en

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    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to an acrylic thermoplastic resin composition excellent in transparency, heat resistance and weather resistance, and having a highly controlled birefringence, and a molded product thereof.
  • methacrylic resin represented by homopolymer of methyl methacrylate (PMMA), polystyrene (PS), styrene / methyl methacrylate copolymer (MS), polycarbonate (PC), etc.
  • PMMA methyl methacrylate
  • PS polystyrene
  • MS styrene / methyl methacrylate copolymer
  • PC polycarbonate
  • methacrylic resins have been applied to industrial fields such as signboards, lighting covers, automobile parts, decorative articles and the like because of their excellent transparency, surface hardness, weather resistance, etc. and good moldability.
  • the birefringence which is an optical characteristic is small, it has been applied as an optical resin for optical materials such as an optical disk, an optical film, and a plastic substrate.
  • optical resins for optical materials are not only excellent in transparency but also birefringence such as high heat resistance, weather resistance, low birefringence and significant phase difference. Control is becoming necessary.
  • Patent Document 1 describes a styrene copolymer comprising a predetermined amount of styrene, maleic anhydride and methyl methacrylate as a transparent novel styrene copolymer having improved heat resistance.
  • Patent Documents 2 and 3 disclose copolymers obtained by polymerizing a structural mixture having methyl methacrylate, maleic anhydride and styrene in a predetermined ratio as copolymers having excellent heat distortion resistance and water resistance. Are listed.
  • Patent Document 4 discloses a method for producing a heat-resistant acrylic resin having good optical purity by washing a copolymer comprising a predetermined amount of a methyl methacrylate unit and an N-alkyl-substituted maleimide unit by a predetermined method.
  • Patent Document 5 describes a copolymer of a structural mixture comprising a predetermined amount of methyl methacrylate, N-arylmaleimide and an aromatic vinyl compound as a heat-resistant resin.
  • the opportunity to view the display screen not only from the front but also from an oblique direction is increasing.
  • the principle of the display device due to the principle of the display device, there arises a problem that the display color change and the contrast are lowered depending on the viewing direction.
  • an optical film material is required, and a technique for controlling the birefringence of the optical film to almost zero and a technique for controlling it to be significantly positive or significantly negative are required.
  • Non-Patent Documents 1 and 2 are optical materials which have a small change in birefringence due to an external force, that is, a small absolute value of the photoelastic coefficient.
  • the copolymer can simultaneously control the birefringence and the photoelastic coefficient, and can simultaneously set the absolute value of the birefringence and the photoelastic coefficient to zero (zero-zero birefringence), but the heat resistance is insufficient. There was a problem.
  • Patent Document 6 discloses a maleimide copolymer obtained by copolymerizing a predetermined amount of a methacrylic acid ester structure, a maleimide structure, and an aromatic vinyl structure, and a methacrylic acid ester structure and an aromatic vinyl structure.
  • a thermoplastic resin composition containing a copolymer obtained by copolymerization in a predetermined amount is described.
  • Patent Document 7 discloses a transparent heat resistant resin composition obtained by copolymerizing a copolymer obtained by polymerizing a predetermined amount of methacrylic acid ester and a predetermined amount of N-substituted maleimide (substituent is an aromatic derivative).
  • Patent Document 8 discloses a transparent heat-resistant methacrylic resin composition comprising a predetermined amount of a copolymer of a structural mixture comprising methyl methacrylate, N-cyclohexylmaleimide and an aromatic vinyl compound, and a predetermined amount of methyl methacrylate. And a methacrylic resin composition each containing a polymer in a predetermined ratio.
  • Patent Document 9 discloses a thermoplastic resin composition excellent in heat resistance, water resistance, and impact resistance, obtained by polymerizing a specific amount of a specific maleimide compound, methyl methacrylate, or a specific methacrylate ester. A thermoplastic resin composition comprising a copolymer and an MMA polymer containing a predetermined amount of methyl methacrylate is described.
  • Patent Document 10 comprises 70 to 85% by weight of methyl methacrylate monomer units and 15 to 30% by weight of N-substituted maleimide compound monomer units, and has an intrinsic birefringence of ⁇ 0.002 to +0 at room temperature. A copolymer of 0.002 is disclosed.
  • Patent Document 6 discloses only an example using N-cyclohexylmaleimide as a maleimide structure, and it is further limited that N-cyclohexylmaleimide is preferable in order to impart desired heat resistance and optical properties.
  • the thermoplastic resin composition described in Patent Document 6 is not focused on optical properties other than the total light transmittance, turbidity (haze), and yellowing degree (YI), and birefringence is not discussed. It has not been evaluated.
  • the heat resistance also has a problem that it is not necessarily sufficient as the currently required heat resistance.
  • Patent Document 7 only describes an example using a maleimide having an aromatic derivative as a substituent as a maleimide structure, and discloses optical properties (transparency, low birefringence, etc.).
  • the birefringence of the disk substrate as an injection-molded body is only evaluated, and no suggestion is given regarding the birefringence distribution in the molded body.
  • Patent Document 8 discloses transparency (total light transmittance, turbidity (haze), yellowing degree (YI)), but does not provide any suggestion regarding birefringence. Further, Patent Document 9 has no disclosure that gives suggestions regarding transparency (total light transmittance, turbidity (haze), yellowing degree (YI)) and birefringence.
  • Patent Document 10 describes the intrinsic birefringence, but there is no suggestion regarding the photoelastic coefficient, and the optical characteristics are not necessarily sufficient.
  • an acrylic thermoplastic resin composition having excellent transparency, heat resistance, and weather resistance, and having highly controlled optical properties (birefringence and photoelastic coefficient), and There is no technology that can provide a molded article.
  • the present invention provides an acrylic thermoplastic resin composition that is excellent in transparency, heat resistance, and weather resistance, and whose optical properties (birefringence and photoelastic coefficient) are highly controlled, and the acrylic thermoplastic resin. It aims at providing the molded object which consists of a composition.
  • the present invention has found the surprising fact that a specific acrylic thermoplastic resin composition is excellent in transparency, heat resistance and weather resistance, and its birefringence is highly controlled.
  • the total content of the first unit is 50 to 95% by mass based on the total amount of the first acrylic resin and the second acrylic resin, and the second structural unit and the third structure
  • An acrylic thermoplastic resin composition having a total content of units of 5 to 50% by mass.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an arylalkyl group having 7 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or And an aryl group having 6 to 14 carbon atoms and having at least one substituent selected from Group A below.
  • Group A a halogen atom, a hydroxyl group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms.
  • R 2 represents an arylalkyl group having 7 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aryl group having 6 to 14 carbon atoms having at least one substituent selected from the following group B:
  • R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 14 carbon atoms.
  • Group B halogen atom, hydroxyl group, nitro group, alkoxy group having 1 to 12 carbon atoms, alkyl group having 1 to 12 carbon atoms and arylalkyl group having 7 to 14 carbon atoms.
  • R 5 represents a hydrogen atom, a cycloalkyl group having 3 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or a carbon number of 1 to 12 having at least one substituent selected from the following group C:
  • R 6 and R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 14 carbon atoms.
  • Group C halogen atom, hydroxyl group, nitro group and alkoxy group having 1 to 12 carbon atoms.
  • the content of the second structural unit is 0.1 to 49.9% by mass based on the total amount of the first acrylic resin and the second acrylic resin, and the third structure
  • the first acrylic resin has 50 to 95% by mass of the first structural unit and 5 to 50% by mass of the second structural unit, based on the total amount thereof. 2].
  • the second acrylic resin has 50 to 95% by mass of the first structural unit and 5 to 50% by mass of the third structural unit, based on the total amount thereof.
  • R 1 is a methyl group or a benzyl group
  • R 2 is a phenyl group or a phenyl group having at least one substituent selected from the group B
  • the first acrylic resin has a weight average molecular weight Mw in terms of polymethyl methacrylate measured by GPC measurement method of 3000 to 1000000, and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is The acrylic thermoplastic resin composition according to any one of [1] to [5], which is 1 to 10.
  • the second acrylic resin has a weight average molecular weight Mw in terms of polymethyl methacrylate measured by GPC measurement method of 3,000 to 1,000,000, and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is
  • [17] A film-like or sheet-like molded article obtained by stretching a resin sheet made of the acrylic thermoplastic resin according to any one of [1] to [13] formed by solution casting at least in a uniaxial direction. .
  • a polarizing plate protective film comprising the molded product according to any one of [14] to [17].
  • a retardation film comprising the molded article according to any one of [14] to [17].
  • a retardation film comprising the molded product according to any one of [14] to [17].
  • a retardation film comprising the molded product according to any one of [14] to [17].
  • a transparent plastic substrate comprising the molded product according to any one of [14] to [17].
  • a lens comprising the molded article according to any one of [14] to [17].
  • an acrylic thermoplastic resin composition having excellent transparency, heat resistance and weather resistance, and having highly controlled optical properties (birefringence and photoelastic coefficient), and the acrylic thermoplastic resin composition It is possible to provide an adult liquid composed of a product.
  • FIG. 3 is a diagram showing a 1 H-NMR spectrum of an acrylic thermoplastic resin composition of Example 3. It is a figure which shows a 3 step
  • the acrylic thermoplastic resin composition includes a first acrylic resin having a first structural unit and a second structural unit, and a second having a first structural unit and a third structural unit. An acrylic resin.
  • the total content of the first structural unit is 50 to 95% by mass based on the total amount of the first acrylic resin and the second acrylic resin.
  • the total content of the second structural unit and the third structural unit is 5 to 50% by mass.
  • the first acrylic resin of the present embodiment has a first structural unit and a second structural unit.
  • the first structural unit is a structural unit represented by the following formula (1).
  • R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an arylalkyl group having 7 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or And an aryl group having 6 to 14 carbon atoms and having at least one substituent selected from Group A below.
  • the group A is a group consisting of a halogen atom, a hydroxyl group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms.
  • the alkyl group may be linear or branched. Further, the alkyl group in the arylalkyl group and the alkyl group in the alkoxy group may be linear or branched.
  • the alkyl group having 1 to 12 carbon atoms in R 1 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • Examples of the alkyl group having 1 to 12 carbon atoms in R 1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, and nonyl group.
  • a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group are included in that the transparency and weather resistance of the acrylic thermoplastic resin are further improved.
  • Group, isobutyl group, t-butyl group and 2-ethylhexyl group are preferable, and methyl group is more preferable.
  • Examples of the cycloalkyl group having 5 to 12 carbon atoms in R 1 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, a bicyclooctyl group, a tricyclododecyl group, an isobornyl group, and an adamantyl group. And tetracyclododecyl group.
  • a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a tricyclodecyl group, a bicyclooctyl group, a tricyclododecyl group, and an isobornyl group are preferable.
  • Examples of the arylalkyl group having 7 to 14 carbon atoms in R 1 include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a 6-phenylhexyl group, and an 8-phenyloctyl group. Of these, benzyl, 1-phenylethyl, 2-phenylethyl, and 3-phenylpropyl are preferred.
  • examples of the aryl group having 6 to 14 carbon atoms in R 1 include a phenyl group, a naphthyl group, and an anthracenyl group, and among these, a phenyl group is preferable.
  • R 1 may be an aryl group having 6 to 14 carbon atoms having a substituent, wherein the substituent is a halogen atom, a hydroxyl group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, or 1 carbon atom.
  • the aryl group having 6 to 14 carbon atoms having a substituent is preferably a phenyl group having a substituent.
  • the aryl group having 6 to 14 carbon atoms having a substituent include 2,4,6-tribromophenyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 4-bromophenyl group, 2-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 4-ethylphenyl group, 2-methoxyphenyl group, 4-methoxyphenyl group, 2-nitrophenyl group, 4-nitrophenyl group, 2, Examples include 4,6-trimethylphenyl group. Among these, 2,4,6-tribromophenyl group is preferable in terms of imparting flame retardancy.
  • the content of the first structural unit in the first acrylic resin is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, based on the total amount of the first acrylic resin. It is preferably 70 to 90% by mass.
  • the first acrylic resin may contain only one kind of the first structural unit, or may contain two or more kinds of the first structural unit.
  • the first acrylic resin may have a structural unit in which R 1 is an alkyl group and a structural unit in which R 1 is an arylalkyl group or an aryl group.
  • the content of the latter structural unit is preferably 0.1 to 10% by mass, more preferably 0.1 to 8% by mass, based on the total amount of the first acrylic resin, More preferably, the content is 1 to 6% by mass. According to the first acrylic resin in this range, an effect of improving optical characteristics such as birefringence can be obtained without a large decrease in heat resistance.
  • the first structural unit is formed from, for example, a first monomer selected from methacrylic acid monomers and methacrylic acid esters.
  • the first monomer can be represented by the following formula (1-a).
  • R 1 has the same meaning as R 1 in Formula (1).
  • methacrylic acid esters examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate and the like.
  • Methacrylic acid alkyl ester methacrylic acid cycloalkyl ester such as cyclopentyl methacrylate, cyclohexyl methacrylate, cyclooctyl methacrylate, tricyclodecyl methacrylate, bicyclooctyl methacrylate, tricyclododecyl methacrylate, isobornyl methacrylate; phenyl methacrylate, Benzyl methacrylate, 1-phenylethyl methacrylate, 2-phenylethyl methacrylate, 3-phenylpropyl methacrylate, methacrylic acid 2 Methacrylic acid aryl based ester such as 4,6-tribromophenyl; and the like. These first monomers may be used alone or in combination of two or more.
  • the second structural unit is a structural unit represented by the following formula (2).
  • R 2 represents an arylalkyl group having 7 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aryl group having 6 to 14 carbon atoms having at least one substituent selected from the following group B;
  • R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 14 carbon atoms.
  • Group B is a group consisting of a halogen atom, a hydroxyl group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, and an arylalkyl group having 7 to 14 carbon atoms.
  • Examples of the arylalkyl group having 7 to 14 carbon atoms in R 2 include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a 6-phenylhexyl group, and an 8-phenyloctyl group.
  • a benzyl group is preferred in terms of further improving optical properties such as heat resistance and low birefringence.
  • Examples of the aryl group having 6 to 14 carbon atoms in R 2 include a phenyl group, a naphthyl group, and an anthracenyl group, and among these, the optical characteristics such as heat resistance and low birefringence are further improved.
  • a phenyl group is preferred.
  • R 2 may be a C 6-14 aryl group having a substituent, wherein the substituent is a halogen atom, hydroxyl group, nitro group, C 1-12 alkoxy group, C 1 A group selected from the group consisting of an alkyl group having ⁇ 12 and an arylalkyl group having 7 to 14 carbon atoms (group B).
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkoxy group having 1 to 12 carbon atoms as a substituent, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms is more preferable.
  • substituent having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, and 2-ethylhexyl. Examples thereof include an oxy group, a 1-decyloxy group, and a 1-dodecyloxy group.
  • alkyl group having 1 to 12 carbon atoms and the arylalkyl group having 7 to 14 carbon atoms as the substituent are exemplified as the alkyl group having 1 to 12 carbon atoms and the arylalkyl group having 7 to 14 carbon atoms in R 1 .
  • Groups are exemplified as well.
  • the aryl group having 6 to 14 carbon atoms having a substituent is preferably a phenyl group having a substituent or a naphthyl group having a substituent.
  • the aryl group having 6 to 14 carbon atoms having a substituent include 2,4,6-tribromophenyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 4-bromophenyl group, 2-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 4-ethylphenyl group, 2-methoxyphenyl group, 4-methoxyphenyl group, 2-nitrophenyl group, 4-nitrophenyl group, 2, Examples include 4,6-trimethylphenyl group. Among these, 2,4,6-tribromophenyl group is preferable in terms of imparting flame retardancy.
  • alkyl group having 1 to 12 carbon atoms in R 3 and R 4 an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
  • Examples of the alkyl group having 1 to 12 carbon atoms in R 3 and R 4 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and a 2-ethylhexyl group. , Nonyl group, decanyl group, lauryl group, etc.
  • Examples of the aryl group having 6 to 14 carbon atoms in R 3 and R 4 include a phenyl group, a naphthyl group, and an anthracenyl group. Among these, optical characteristics such as heat resistance and low birefringence are further improved. In this respect, a phenyl group is preferred.
  • R 3 and R 4 are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and more preferably a hydrogen atom.
  • the content of the second structural unit in the first acrylic resin is preferably 0.1 to 49.9% by mass based on the total amount of the first acrylic resin, and preferably 0.1 to 35% by mass. % Is more preferable, and 0.1 to 20% by mass is even more preferable.
  • the first acrylic resin may contain only one kind of the second structural unit, or may contain two or more kinds of the second structural unit.
  • the second structural unit is formed of, for example, a second monomer selected from N-substituted maleimide compounds represented by the following formula (2-a).
  • R 2, R 3 and R 4 have the same meaning as R 2, R 3 and R 4 in each formula (2).
  • Examples of the second monomer include N-phenylmaleimide, N-benzylmaleimide, N- (2-chlorophenyl) maleimide, N- (4-chlorophenyl) maleimide, N- (4-bromophenyl) maleimide, N- ( 2-methylphenyl) maleimide, N- (2-ethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N- (2-nitrophenyl) maleimide, N- (2,4,6-trimethylphenyl) maleimide N- (4-benzylphenyl) maleimide, N- (2,4,6-tribromophenyl) maleimide, N-naphthylmaleimide, N-anthracenylmaleimide, 3-methyl-1-phenyl-1H-pyrrole 2,5-dione, 3,4-dimethyl-1-phenyl-1H-pyrrole-2,5-dione, 1,3-dione En
  • the first acrylic resin may further contain a structural unit other than the above.
  • the first acrylic resin is a structural unit derived from another monomer that can be copolymerized with the first monomer and the second monomer within a range that does not impair the object of the invention. Furthermore, you may have.
  • a structural unit that does not correspond to any of the first structural unit, the second structural unit, and a third structural unit described later is referred to as a fourth structure. It is called a unit.
  • Other monomers that can be copolymerized include aromatic vinyl; unsaturated nitrile; cyclohexyl group, benzyl group, or acrylic acid ester having an alkyl group having 1 to 18 carbon atoms; olefin; diene; vinyl ether; vinyl ester; Examples thereof include vinyl chloride; allyl ester or methallyl ester of saturated fatty acid monocarboxylic acid such as allyl propionate; polyvalent (meth) acrylate; polyvalent arylate; glycidyl compound; unsaturated carboxylic acid.
  • the other monomer may be one or a combination of two or more selected from these groups.
  • Examples of the aromatic vinyl include styrene, ⁇ -methylstyrene, divinylbenzene and the like.
  • Examples of the unsaturated nitrile include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and the like.
  • acrylic acid ester examples include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, acrylic acid Examples include octyl, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, cyclohexyl acrylate, and benzyl acrylate.
  • examples of the olefin include ethylene, propylene, isobutylene, diisobutylene and the like.
  • examples of the diene include butadiene and isoprene.
  • examples of the vinyl ether include methyl vinyl ether and butyl vinyl ether.
  • examples of the vinyl ester include vinyl acetate and vinyl propionate.
  • examples of the vinyl fluoride include vinylidene fluoride.
  • polyvalent (meth) acrylate examples include ethylene glycol (meth) acrylate, diethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, di (meth) acrylate of bisphenol A ethylene oxide or propylene oxide adduct, di (meth) acrylate of ethylene oxide or propylene oxide adduct of halogenated bisphenol A, ethylene oxide or propylene of isocyanurate Examples thereof include di- or tri (meth) acrylates of oxide adducts.
  • Examples of the polyvalent arylate monomer include diallyl phthalate and triallyl isocyanurate.
  • Examples of the glycidyl compound monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
  • Examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and half-esterified products or anhydrides thereof.
  • the content of the fourth structural unit in the first acrylic resin is preferably 0.1 to 20% by mass, and preferably 0.1 to 15% by mass based on the total amount of the first acrylic resin. More preferably, it is 0.1 to 10% by mass. If the content of the fourth structural unit is in the above range, the hygroscopicity of the acrylic thermoplastic resin composition is improved. From the viewpoint of weather resistance, the content of the fourth structural unit is preferably less than 10% by mass, and more preferably less than 7% by weight.
  • the first acrylic resin may have only one kind of the fourth structural unit, or may have two or more kinds of the fourth structural unit.
  • An example of the fourth structural unit is a structural unit represented by the following formula (4).
  • R 8 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms
  • R 9 represents a halogen atom, a hydroxyl group, a nitro group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
  • A represents an integer of 1 to 3.
  • alkyl group having 1 to 12 carbon atoms in R 8 an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.
  • Examples of the alkyl group having 1 to 12 carbon atoms for R 8 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, 1- Examples thereof include a decyl group and a 1-dodecyl group, and among these, a methyl group is preferred.
  • halogen atom for R 9 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group having 1 to 12 carbon atoms in R 9 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.
  • Examples of the alkyl group having 1 to 12 carbon atoms for R 9 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, 1- Decyl group, 1-dodecyl group and the like.
  • methyl group, ethyl group, n-propyl group, isopropyl group, n- A butyl group, an isobutyl group, a t-butyl group, and a 2-ethylhexyl group are preferable, and a methyl group is more preferable.
  • the alkoxy group having 1 to 12 carbon atoms in R 9 is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 8 carbon atoms.
  • the substituent having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, and 2-ethylhexyl. Examples thereof include an oxy group, a 1-decyloxy group, and a 1-dodecyloxy group, and among these, a methoxy group is preferable.
  • the structural unit represented by the formula (4) can be formed, for example, from a monomer represented by the following formula (4-a).
  • R 8, R 9 and a have the same meanings as R 8, R 9 and a in each formula (4).
  • Examples of the monomer represented by the formula (4-a) include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2 -Methyl-4-chlorostyrene, 2,4,6-trimethylstyrene, ⁇ -methylstyrene, cis- ⁇ -methylstyrene, trans- ⁇ -methylstyrene, 4-methyl- ⁇ -methylstyrene, 4-fluoro- ⁇ -Methylstyrene, 4-chloro- ⁇ -methylstyrene, 4-bromo- ⁇ -methylstyrene, 4-t-butylstyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 2,4-difluorostyrene 2-chlorostyrene, 3-chlorostyrene, 4-ch
  • the weight average molecular weight Mw in terms of polymethylmethacrylate by GPC measurement method of the first acrylic resin is preferably 3000 to 1000000. When the weight average molecular weight Mw is within the above range, sufficient strength can be imparted to the acrylic thermoplastic resin composition, and the strength of the molded article of the acrylic thermoplastic resin composition is improved.
  • the weight average molecular weight Mw is more preferably from 4,000 to 800,000, still more preferably from 5,000 to 500,000.
  • the molecular weight distribution (Mw / Mn) in terms of polymethyl methacrylate by GPC measurement method of the first acrylic resin is preferably 1-10, and the acrylic thermoplastic resin composition has a resin viscosity suitable for molding processing. From the viewpoint of imparting, 1.1 to 7.0 is more preferable, 1.2 to 5.0 is more preferable, and 1.5 to 4.0 can also be achieved.
  • the glass transition temperature (Tg) of the first acrylic resin is preferably 120 ° C. or higher. If Tg is 120 ° C. or higher, it has necessary and sufficient heat resistance as a recent lens molded body and liquid crystal display film molded body. Tg is preferably 130 ° C. or higher, more preferably 135 ° C. or higher. On the other hand, the upper limit of Tg is preferably 180 ° C. or lower.
  • a preferred embodiment of the first acrylic resin is shown below.
  • the first acrylic resin of this embodiment is a resin composed of a structural unit selected from the group consisting of a first structural unit, a second structural unit, and a fourth structural unit, and the first acrylic resin Based on the total amount of resin, the content of the first structural unit is 50 to 95% by mass, the content of the second structural unit is 5 to 50% by mass, and the content of the fourth structural unit is 0. ⁇ 20% by weight.
  • the first acrylic resin of this embodiment is composed of structural units selected from the group consisting of the first structural unit, the second structural unit, and the fourth structural unit except for both ends, the first acrylic resin
  • the total content of the structural unit, the second structural unit, and the fourth structural unit is about 100% by mass.
  • the first acrylic resin of this embodiment is preferably used in combination with a preferred embodiment of the second acrylic resin described later. Thereby, the effect of this invention is show
  • the second acrylic resin of this embodiment has a first structural unit and a third structural unit.
  • first structural unit of the second acrylic resin examples include the same structural units as those exemplified as the first structural unit of the first acrylic resin.
  • the content of the first structural unit in the second acrylic resin is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, based on the total amount of the second acrylic resin. It is preferably 70 to 90% by mass.
  • the second acrylic resin may have only one first structural unit, or may have two or more first structural units. Further, the second acrylic resin may have the same type of structural unit as the first structural unit contained in the first acrylic resin as the first structural unit. It may have a structural unit different from the first structural unit contained in.
  • the third structural unit is a structural unit represented by the following formula (3).
  • R 5 is a hydrogen atom, a cycloalkyl group having 3 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or a C 1-12 carbon atom having at least one substituent selected from the following group C.
  • An alkyl group, and R 6 and R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 14 carbon atoms.
  • Group C is a group consisting of a halogen atom, a hydroxyl group, a nitro group, and an alkoxy group having 1 to 12 carbon atoms.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms in R 5 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, a bicyclooctyl group, a tricyclododecyl group, An isobornyl group, an adamantyl group, a tetracyclododecyl group and the like can be mentioned.
  • a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are preferable, and an acrylic thermoplastic resin composition
  • a cyclohexyl group is more preferable in terms of further improving optical properties such as weather resistance and transparency of the product and providing low water absorption to the acrylic thermoplastic resin composition.
  • the alkyl group having 1 to 12 carbon atoms in R 5 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.
  • Examples of the alkyl group having 1 to 12 carbon atoms in R 5 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n- Hexyl group, n-octyl group, n-dodecyl group, n-octadecyl group, 2-ethylhexyl group, 1-decyl group, 1-dodecyl group and the like.
  • the weather resistance of the acrylic thermoplastic resin composition A methyl group, an ethyl group, and an isopropyl group are preferable because optical properties such as transparency and transparency are further improved.
  • R 5 may be an alkyl group having 1 to 12 carbon atoms having a substituent, wherein the substituent is a group consisting of a halogen atom, a hydroxyl group, a nitro group, and an alkoxy group having 1 to 12 carbon atoms ( Group C).
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkoxy group having 1 to 12 carbon atoms as a substituent, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms is more preferable.
  • substituent having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, and 2-ethylhexyl. Examples thereof include an oxy group, a 1-decyloxy group, and a 1-dodecyloxy group.
  • examples of the alkyl group having 1 to 12 carbon atoms having a substituent include a dichloromethyl group, a trichloromethyl group, a trifluoroethyl group, and a hydroxyethyl group, and among these, a trifluoroethyl group is preferable. It is.
  • the alkyl group having 1 to 12 carbon atoms in R 6 and R 7 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • Examples of the alkyl group having 1 to 12 carbon atoms in R 6 and R 7 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and a 2-ethylhexyl group. , Nonyl group, decanyl group, lauryl group, etc.
  • Examples of the aryl group having 6 to 14 carbon atoms in R 6 and R 7 include a phenyl group, a naphthyl group, and an anthracenyl group, and among these, optical characteristics such as heat resistance and low birefringence are further improved. In this respect, a phenyl group is preferred.
  • R 6 and R 7 are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and more preferably a hydrogen atom.
  • the content of the third structural unit in the second acrylic resin is preferably 0.1 to 49.9% by mass based on the total amount of the second acrylic resin, and preferably 0.1 to 40% by mass. % Is more preferable, and 0.1 to 35% by mass is even more preferable.
  • the second acrylic resin may contain only one third structural unit, or may contain two or more third structural units.
  • the third structural unit is formed of, for example, a third monomer selected from N-substituted maleimide compounds represented by the following formula (3-a).
  • R 5, R 6 and R 7 have the same meanings as R 5, R 6 and R 7 in each formula (3).
  • the second acrylic resin may contain a monomer other than the above.
  • the second acrylic resin contains structural units derived from other monomers copolymerizable with the first monomer and the third monomer within the range not impairing the object of the invention. , May further be included.
  • structural units other than the first, second, and third structural units in the second acrylic resin are collectively referred to as a fifth structural unit.
  • Examples of the fifth structural unit contained in the second acrylic resin include the same structural units exemplified as the fourth structural unit contained in the first acrylic resin.
  • the second acrylic resin may contain only one kind of the fifth structural unit, or may contain two or more kinds of the fifth structural unit.
  • the second acrylic resin may have the same structural unit as the fourth structural unit of the first acrylic resin as the fifth structural unit, and the first acrylic resin has. It may have a structural unit different from the fourth structural unit.
  • the content of the fifth structural unit in the second acrylic resin is preferably 0.1 to 20% by mass, and preferably 0.1 to 15% by mass, based on the total amount of the second acrylic resin. More preferably, it is 0.1 to 10% by mass.
  • the content of the fifth structural unit is in the above range, the hygroscopicity of the acrylic thermoplastic resin composition is improved. From the viewpoint of weather resistance, the content of the fifth structural unit is preferably less than 10% by mass, and more preferably less than 7% by weight.
  • the weight average molecular weight Mw in terms of polymethylmethacrylate by GPC measurement method of the second acrylic resin is preferably 3000 to 1000000. When the weight average molecular weight Mw is within the above range, sufficient strength can be imparted to the acrylic thermoplastic resin composition, and the strength of the molded article of the acrylic thermoplastic resin composition is improved.
  • the weight average molecular weight Mw is more preferably from 4,000 to 800,000, still more preferably from 5,000 to 500,000.
  • the molecular weight distribution (Mw / Mn) in terms of polymethyl methacrylate by GPC measurement method of the second acrylic resin is preferably 1 to 10, and the acrylic thermoplastic resin composition has a resin viscosity suitable for molding processing. From the viewpoint of imparting, 1.1 to 7.0 is more preferable, 1.2 to 5.0 is more preferable, and 1.5 to 4.0 can also be achieved.
  • the glass transition temperature (Tg) of the second acrylic resin is preferably 120 ° C. or higher. If Tg is 120 ° C. or higher, it has necessary and sufficient heat resistance as a recent lens molded body and liquid crystal display film molded body. Tg is preferably 130 ° C. or higher, more preferably 135 ° C. or higher. On the other hand, the upper limit of Tg is preferably 180 ° C. or lower.
  • a preferred embodiment of the second acrylic resin is shown below.
  • the second acrylic resin of this embodiment is a resin composed of a structural unit selected from the group consisting of a first structural unit, a third structural unit, and a fifth structural unit, and the second acrylic resin Based on the total amount of the resin, the content of the first structural unit is 50 to 95% by mass, the content of the third structural unit is 5 to 50% by mass, and the content of the fifth structural unit is 0. ⁇ 20% by weight.
  • the second acrylic resin of this embodiment is composed of structural units selected from the group consisting of the first structural unit, the third structural unit, and the fifth structural unit except for both ends.
  • the total content of the structural unit, the third structural unit, and the fifth structural unit is about 100% by mass.
  • the second acrylic resin of this embodiment is preferably used in combination with a preferred embodiment of the first acrylic resin described above. Thereby, the effect of this invention is show
  • Both the first acrylic resin and the second acrylic resin can be obtained by the following polymerization step. Moreover, it can refine
  • the first acrylic resin can be obtained by polymerizing the monomer (A) containing the first monomer and the second monomer.
  • the second acrylic resin can be obtained by polymerizing the monomer (B) containing the first monomer and the third monomer.
  • the polymerization method for example, generally used polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, living radical polymerization, and anionic polymerization can be used.
  • the polymerization method of the acrylic resin includes cast polymerization without using a suspending agent or an emulsifier. It is desirable to use solution polymerization.
  • the polymerization mode for example, either a batch polymerization method or a continuous polymerization method can be used.
  • the batch polymerization method is desirable from the viewpoint of simple polymerization operation, and the continuous polymerization method is desirably used from the viewpoint of obtaining a polymer having a more uniform composition.
  • the temperature at the time of the polymerization reaction and the polymerization time can be appropriately adjusted according to the type and ratio of the monomer to be used.
  • the polymerization temperature is 80 to 150 ° C.
  • the polymerization time is 1 to 12 hours.
  • examples of the polymerization solvent include aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ether solvents such as tetrahydrofuran; It is done. These solvents may be used alone or in combination of two or more. If the boiling point of the solvent to be used is too high, the residual volatile content of the finally obtained acrylic thermoplastic resin composition will increase. Therefore, a solvent having a boiling point of 50 to 200 ° C. is preferred.
  • a polymerization initiator may be added as necessary.
  • any initiator generally used in radical polymerization can be used.
  • Organic peroxides such as oxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexane) Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo compounds such as dimethyl-2,2′-azobisisobutyrate;
  • These polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator used may be appropriately set according to the combination of monomers and reaction conditions, and is not particularly limited, but is preferably used in the range of 0.005 to 5% by mass.
  • molecular weight regulator used as necessary in the polymerization reaction, any one used in general radical polymerization is used, and for example, mercaptan compounds such as butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-ethylhexyl thioglycolate are particularly preferable. It is mentioned as preferable.
  • mercaptan compounds such as butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-ethylhexyl thioglycolate are particularly preferable. It is mentioned as preferable.
  • These molecular weight regulators are added in a concentration range such that the degree of polymerization is controlled within the aforementioned range.
  • an organic phosphorus compound or an organic acid may be added as necessary during the polymerization reaction.
  • favorable effects such as suppression of side reactions and reduction of the amount of unreacted N-substituted maleimide can be expected.
  • organic phosphorus compound examples include alkyl (aryl) phosphonous acid and diesters or monoesters thereof; dialkyl (aryl) phosphinic acid and esters thereof; alkyl (aryl) phosphonic acids and diesters or monoesters thereof; alkyl Phosphinic acid and esters thereof; phosphorous acid diester, phosphorous acid monoester, phosphorous acid triester; phosphoric acid diester, phosphoric acid monoester, phosphoric acid triester and the like.
  • organophosphorus compounds may be used alone or in combination of two or more.
  • the amount of the organophosphorus compound used is preferably 0.001 to 5.0 mass% with respect to the total amount of monomers.
  • organic acid for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, cyclohexanecarboxylic acid, Examples thereof include phthalic acid, isophthalic acid, terephthalic acid and the like, and acid anhydrides thereof. These organic acids may be used alone or in combination of two or more. The amount of the organic acid used is preferably 0.001 to 1.0% by mass with respect to the total amount of monomers.
  • the polymer concentration is 10% by mass or more and 95% by mass or less.
  • the polymer concentration is 10% by mass or more, the molecular weight and the molecular weight distribution can be easily adjusted, and when the polymer concentration is 95% by mass or less, a high molecular weight polymer can be obtained.
  • the polymer concentration is preferably 75% by mass or less, more preferably 60% by mass or less.
  • a polymerization solvent as appropriate from the viewpoint of appropriately maintaining the viscosity of the obtained polymerization reaction solution.
  • the reaction solution viscosity By maintaining the reaction solution viscosity appropriately, it is easy to control heat removal, and microgel generation in the reaction solution can be suppressed.
  • the polymer concentration in the latter half of the polymerization reaction in which the viscosity increases, it is preferable to control the polymer concentration to be 50% by mass or less by appropriately adding a polymerization solvent.
  • the form of appropriately adding the polymerization solvent to the polymerization reaction solution is not particularly limited, and for example, the polymerization solvent may be added continuously or the polymerization solvent may be added intermittently.
  • the concentration of the acrylic resin produced in the polymerization reaction solution in this way, the temperature uniformity inside the reactor can be improved and the gelation of the reaction solution can be more sufficiently suppressed.
  • the polymerization solvent to be added may be, for example, the same type of solvent used during the initial charging of the polymerization reaction or a different type of solvent, but the solvent used during the initial charging of the polymerization reaction. It is preferable to use the same type of solvent.
  • the polymerization solvent to be added may be only one kind of single solvent or two or more kinds of mixed solvents.
  • the acrylic resin When the acrylic resin is polymerized by the suspension polymerization method, it is carried out in an aqueous medium, and a suspending agent and, if necessary, a suspending aid are added.
  • the suspending agent include water-soluble polymers such as polyvinyl alcohol, methylcellulose, and polyacrylamide, and inorganic substances such as calcium phosphate and magnesium pyrophosphate.
  • the water-soluble polymer is preferably used in an amount of 0.03 to 1% by weight based on the total amount of monomers, and the inorganic substance is used in an amount of 0.05 to 0.5% by weight based on the total amount of monomers. Is preferred.
  • the suspension aid there are anionic surfactants such as sodium dodecylbenzenesulfonate.
  • an inorganic substance is used as the suspension agent, it is preferable to use a suspension aid.
  • the suspension aid is preferably used in an amount of 0.001 to 0.02% by mass based on the total amount of monomers.
  • the devolatilization step means a step of removing a volatile component such as a polymerization solvent, a residual monomer and moisture under reduced pressure heating conditions as necessary. If this removal treatment is insufficient, residual volatile components in the resulting acrylic resin increase, and coloring due to alteration during molding, or molding defects such as bubbles and silver streaks may occur.
  • the residual volatile content is preferably 0.5% by mass or less, more preferably 0.4% by mass or less, and still more preferably 0.3% by mass or less, with respect to 100% by mass of the acrylic resin.
  • the amount of residual volatile matter corresponds to the total amount of residual monomer, polymerization solvent, and side reaction product that did not react during the polymerization reaction described above.
  • Examples of the apparatus used in the devolatilization step include a devolatilizer composed of a heat exchanger and a devolatilization tank; an extruder with a vent; an apparatus in which the devolatilizer and the extruder are arranged in series.
  • a devolatilizer composed of a heat exchanger and a devolatilization tank
  • an extruder with a vent an apparatus in which the devolatilizer and the extruder are arranged in series.
  • an extruder with a vent one or a plurality of vents may be used, but it is preferable to have a plurality of vents.
  • the temperature in the devolatilization step is preferably 150 to 350 ° C, more preferably 170 to 330 ° C, and further preferably 200 to 300 ° C. If this temperature is less than 150 ° C., the residual volatile matter may increase. Conversely, when this temperature exceeds 350 ° C., the resulting acrylic resin may be colored or decomposed.
  • the pressure in the devolatilization step is preferably 931 to 1.33 hPa (700 to 1 mmHg), more preferably 800 to 13.3 hPa (600 to 10 mmHg), and further preferably 667 to 20.0 hPa (500 to 15 mmHg).
  • this pressure exceeds 931 hPa (700 mmHg)
  • volatile matter may remain easily.
  • the pressure is less than 1.33 hPa (1 mmHg), industrial implementation may be difficult.
  • the treatment time is appropriately selected depending on the amount of residual volatile matter, but a shorter one is preferable in order to suppress coloring and decomposition of the resulting acrylic resin.
  • the monomer reaction conversion rate during the polymerization reaction is low, a large amount of unreacted monomer remains in the polymerization solution. In that case, in order to reduce the residual volatile content of the resulting acrylic resin, the treatment is performed at a high treatment temperature for a long time, but there is a problem that coloring and decomposition are likely to occur.
  • the monomer in question is, for example, an aromatic hydrocarbon solvent, a hydrocarbon solvent, or an alcohol solvent in the polymerization solution.
  • a homogenizer (emulsification / dispersion) treatment is performed, and the unreacted monomer can be separated from the polymerization reaction solution by a pretreatment such as liquid-liquid extraction or solid-liquid extraction.
  • a pretreatment such as liquid-liquid extraction or solid-liquid extraction.
  • the number of foreign substances contained in the acrylic resin is preferably as small as possible when used for optics.
  • an acrylic resin solution or melt is used in a polymerization reaction step, a devolatilization step, and a molding step described later, for example, a leaf disk type polymer filter having a filtration accuracy of 1.5 to 15 ⁇ m. And the like, and the like.
  • the acrylic thermoplastic resin composition contains the first acrylic resin and the second acrylic resin, and is based on the total amount of the first unit based on the total amount of the first acrylic resin and the second acrylic resin.
  • the content is 50 to 95% by mass, and the total content of the second structural unit and the third structural unit is 5 to 50% by mass.
  • the acrylic thermoplastic resin composition contains, as essential components, a second structural unit derived from the first acrylic resin and a third structural unit derived from the second acrylic resin. With such a configuration, the acrylic thermoplastic resin composition exhibits excellent transparency and heat resistance and also exhibits good weather resistance. Furthermore, as a preferable effect, optical characteristics (birefringence and photoelastic coefficient) described later can be highly controlled to a significant value (positive / negative / zero). In other words, in the resin composition containing only one of the first acrylic resin and the second acrylic resin, not only one having insufficient transparency, heat resistance, and weather resistance can be obtained. Also, the control of the optical characteristics is out of the satisfactory range.
  • the first acrylic resin and the second acrylic resin are thermodynamically compatible with each other.
  • the blending ratio (mass ratio) of the first acrylic resin and the second acrylic resin in the acrylic thermoplastic resin composition is preferably in the range of 1/99 to 99/1, more preferably 5/95. To 95/5.
  • the blending ratio can be changed freely within the scope of the present invention, but other physical properties such as transparency and weather resistance can be obtained. Will not be damaged.
  • the difference between the weight average molecular weight of the first acrylic resin and the weight average molecular weight of the second acrylic resin (hereinafter sometimes referred to as “average molecular weight difference”) is set to 10,000 or more, whereby acrylic Workability at the time of molding of the thermoplastic resin composition can be improved.
  • the average molecular weight difference is more preferably 15000 or more, and further preferably 20000 or more.
  • the glass transition temperature of the first acrylic resin is higher than the glass transition temperature of the second acrylic resin, and the glass transition temperature is higher.
  • the acrylic resin is a “high Tg resin” and the acrylic resin having a lower glass transition temperature is a “low Tg resin”
  • the weight average molecular weight of the high Tg resin is smaller than the weight average molecular weight of the low Tg resin. It is preferable.
  • the average molecular weight difference is 10,000 or more and the weight average molecular weight of the high Tg resin is larger than the weight average molecular weight of the low Tg resin, the uniformity during melt mixing is lowered, resulting in a poor appearance of the molded product. There is a case.
  • the combination satisfies the relationship between the above-described Tg and the weight average molecular weight, the uniformity during melt mixing can be more reliably obtained, and the appearance defect of the molded body can be more reliably prevented. it can.
  • an acrylic resin having a relatively low weight average molecular weight (hereinafter sometimes referred to as “low molecular weight body”) is an element that affects the fluidity of the acrylic thermoplastic resin composition, and is relatively heavy.
  • An acrylic resin having a high average molecular weight (hereinafter sometimes referred to as a “high molecular weight body”) is an element that affects the mechanical strength of a molded article made of an acrylic thermoplastic resin composition. The mixed state of the first acrylic resin and the second acrylic resin affects the transparency and appearance of the molded body.
  • the weight average molecular weight of the high Tg resin is 5000 to 400000 (more preferably 10,000 to 300000, and still more preferably 20000 to 250,000).
  • the weight average molecular weight of the low Tg resin is 80,000 to 800,000 (more preferably 90000 to 500,000, more preferably 100000 to 400,000), and the weight average molecular weight of the low Tg resin is 10,000 from the weight average molecular weight of the high Tg resin. It is preferable that it is larger.
  • the weight average molecular weight of the high Tg resin is less than 5,000, the effect of improving the workability is poor, and when it is more than 400,000, the workability may be deteriorated due to a decrease in fluidity. Further, if the weight average molecular weight of the low Tg resin is less than 80,000, the mechanical strength of the molded product may not be sufficiently obtained. If it is greater than 800,000, melt dispersibility cannot be sufficiently obtained and the molded product deteriorates in appearance. There is a fear.
  • the refractive index difference ⁇ d between the refractive index d B of the refractive index of the first acrylic resin d A and second acrylic resin is less than 0.04 Preferably, it is less than 0.03, more preferably less than 0.02. According to the combination satisfying such a refractive index difference ⁇ d, in the acrylic thermoplastic resin composition, a compatible homogeneous phase having further excellent transparency is formed.
  • the first structural unit is preferably contained in a preferential amount over other structural units in order to maintain the excellent transparency, weather resistance and mechanical properties of the methacrylic resin. Therefore, the content of the first structural unit is 50 to 95% by mass based on the total amount of the first acrylic resin and the second acrylic resin. The amount is preferably 60 to 95% by mass, more preferably 65 to 90% by mass, still more preferably 70 to 90% by mass, and most preferably 70 to 85% by mass. When the content of the first structural unit is within this range, the acrylic thermoplastic resin composition is further excellent in transparency, weather resistance and mechanical properties.
  • the total content of the second structural unit and the third structural unit is 5 to 50 mass based on the total amount of the first acrylic resin and the second acrylic resin. %.
  • the amount is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, still more preferably 10 to 30% by mass, and most preferably 15 to 30% by mass.
  • the acrylic thermoplastic resin composition has further improved heat resistance, weather resistance, optical properties (birefringence and light A preferable improvement effect is obtained with respect to the elastic modulus.
  • the content of the second structural unit is preferably 0.1 to 49.9% by mass based on the total amount of the first acrylic resin and the second acrylic resin. More preferably, it is 0.1 to 20% by mass, and further preferably 0.1 to 18% by mass. Most preferably, it is 0.1 to 16% by mass. When the content of the second structural unit is within this range, the acrylic thermoplastic resin composition is further excellent in transparency, weather resistance and mechanical properties.
  • the content of the third structural unit is preferably 0.1 to 49.9% by mass based on the total amount of the first acrylic resin and the second acrylic resin. More preferably, it is 0.1 to 40% by mass, and further preferably 0.1 to 35% by mass. Most preferably, it is 0.1 to 30% by mass. When the content of the third structural unit is within this range, the acrylic thermoplastic resin composition is further excellent in transparency, weather resistance and mechanical properties.
  • the acrylic thermoplastic resin composition contains the fourth structural unit and / or the fifth structural unit, the hygroscopicity tends to be improved.
  • the total content of the fourth structural unit and the fifth structural unit in the acrylic thermoplastic resin composition is preferably 0 to 20% by mass based on the total amount of the first acrylic resin and the second acrylic resin. More preferably, it is 0 to 15% by mass, and further preferably 0 to 10% by mass.
  • the content of the first structural unit is 50 to 95% by mass on the basis of the total amount of the first acrylic resin and the second acrylic resin.
  • the content of the structural unit is 0.1 to 49.9% by mass
  • the content of the third structural unit is 0.1 to 49.9% by mass
  • the fourth structural unit and the fifth structural unit The total content of is preferably 0 to 20% by mass.
  • the content of the first structural unit is 50 to 95% by mass, and the content of the second structural unit is 0.1 to 20 mass%, the content of the third structural unit is 0.1 to 49.9 mass%, and the total content of the fourth structural unit and the fifth structural unit is 0 to 20 mass%. It is more preferable.
  • each structural unit can be calculated based on the blending amount of each acrylic resin by analyzing the first acrylic resin and the second acrylic resin by the NMR method. Moreover, it can obtain
  • the acrylic thermoplastic resin composition according to the present embodiment contains a first acrylic resin and a second acrylic resin, preferably the first acrylic resin and the second acrylic resin are mutually It is a compatible resin composition.
  • the first acrylic resin and the second acrylic resin for example, there is a method of blending by general melt kneading.
  • the kneading temperature varies depending on the blend ratio of both resins and the copolymer composition of the copolymer, but is carried out at 200 to 280 ° C., preferably 200 to 270 ° C., more preferably 200 to 260 ° C. The more it can be melt-kneaded at a lower temperature, the lower the degree of thermal decomposition and coloring.
  • a method for obtaining an acrylic thermoplastic resin composition by performing treatment obtained after dissolving in a solvent (for example, acetone, methyl ethyl ketone, tetrahydrofuran, etc.) capable of simultaneously dissolving the first acrylic resin and the second acrylic resin.
  • a solvent for example, acetone, methyl ethyl ketone, tetrahydrofuran, etc.
  • the acrylic thermoplastic resin composition according to this embodiment may contain various additives as long as the effects of the present invention are not significantly impaired.
  • the type of additive is not particularly limited as long as it is generally used for blending resins and rubber-like polymers.
  • additives include inorganic fillers; pigments such as iron oxides; lubricants and mold release agents such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bisstearamide; paraffinic processes Softeners and plasticizers such as oils, naphthenic process oils, aromatic process oils, paraffins, organic polysiloxanes and mineral oils; hindered phenolic antioxidants, antioxidants such as phosphorus thermal stabilizers, hindered amines Examples thereof include light stabilizers, benzotriazole-based ultraviolet absorbers, flame retardants, antistatic agents; reinforcing agents such as organic fibers, glass fibers, carbon fibers, and metal whiskers; colorants; other additives;
  • the content of the additive is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, and still more preferably 0 to 1% by mass.
  • the acrylic thermoplastic resin composition is within a range that does not impair the object of the present invention.
  • polyolefin resin such as polyethylene and polypropylene; polystyrene, styrene / acrylonitrile copolymer, styrene / maleic anhydride copolymer, styrene / Styrene resin such as methacrylic acid copolymer; Polymethacrylate resin; Polyamide; Polyphenylene sulfide resin; Polyether ether ketone resin; Polyester resin; Polysulfone; Polyphenylene oxide; Polyimide; Polyetherimide; Polyacetal; Resin; Norbornene resin; Thermoplastic resin such as cellulose resin such as triacetyl cellulose; and phenol resin; melamine resin; Silicone resin; Thermosetting resin such as epoxy resin It may contain at least one or more kinds.
  • the acrylic thermoplastic resin composition according to this embodiment preferably has an absolute value of the photoelastic coefficient C of 3.0 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less. more preferably .0 ⁇ 10 -12 Pa -1 or less, further preferably 1.0 ⁇ 10 -12 Pa -1 or less.
  • C R photoelastic coefficient, sigma R is tensile stress
  • is the absolute value of the birefringence
  • nx is the refractive index of stretching direction
  • ny is the refractive index of stretching direction perpendicular to the direction in the plane
  • the photoelastic coefficient of the acrylic thermoplastic resin composition according to the present embodiment is sufficiently smaller than that of existing resins (for example, PMMA, PC, triacetyl cellulose resin, cyclic olefin resin, etc.). Therefore, since it does not cause birefringence due to external force (photoelasticity), it is difficult to undergo birefringence change. In addition, since birefringence caused by residual stress at the time of molding (photoelasticity) hardly occurs, the birefringence distribution in the molded body is also small.
  • existing resins for example, PMMA, PC, triacetyl cellulose resin, cyclic olefin resin, etc.
  • ⁇ n (S) represents birefringence
  • S represents the draw ratio
  • the birefringence ⁇ n (S) is a value obtained by converting a value measured by a film (value obtained by the above formula (i-2)) into a thickness of 100 ⁇ m.
  • C in the formula (ii-a) is a constant and indicates birefringence when not stretched.
  • ) of the slope K is more preferably 0.15 ⁇ 10 ⁇ 5 or less, and further preferably 0.10 ⁇ 10 ⁇ 5 or less.
  • the value of K is a value obtained by measuring the glass transition temperature (Tg) by DSC measurement of the acrylic thermoplastic resin composition and performing uniaxial stretching at a stretching temperature of (Tg + 20) ° C. and a stretching speed of 500 mm / min. Is the value of
  • the value of K is, for example, the value of birefringence ( ⁇ n (S)) expressed in a uniaxially stretched film obtained by stretching the stretching ratio (S) to 100%, 200%, and 300%, respectively. These values can be calculated by plotting them against the draw ratio and approximating the least squares method.
  • the draw ratio (S) is a value represented by the following formula, where L 0 is the distance between chucks before stretching and L 1 is the distance between chucks after stretching.
  • a film-like or sheet-like molded body may be stretched for the purpose of increasing mechanical strength.
  • the value of the slope K represents the magnitude of the change in birefringence ( ⁇ n (S)) with respect to the draw ratio (S), and the greater the K, the greater the amount of change in birefringence with respect to stretching. The smaller the value, the smaller the amount of change in birefringence with respect to stretching.
  • the value of the slope K of the acrylic thermoplastic resin composition according to the present embodiment is sufficiently small compared to existing resins (for example, PMMA, PC, triacetyl cellulose resin, cyclic olefin resin, etc.). Therefore, the existing resin has a characteristic that birefringence increases due to the stretch orientation during the stretching process, whereas the birefringence hardly increases even if the stretching process is performed.
  • existing resins for example, PMMA, PC, triacetyl cellulose resin, cyclic olefin resin, etc.
  • phase difference Re In-plane phase difference Re
  • the absolute value of the retardation Re in the in-plane direction is preferably 30 nm or less.
  • the phase difference Re is a value obtained by converting a value measured as a film (or sheet) into a thickness of 100 ⁇ m.
  • the absolute value of the phase difference Re is more preferably 20 nm or less, further preferably 15 nm or less, and particularly preferably 11 nm or less.
  • the absolute value of the phase difference Re is an index representing the magnitude of birefringence.
  • the acrylic thermoplastic resin composition according to this embodiment is sufficiently small with respect to the birefringence of existing resins (for example, PMMA, PC, triacetyl cellulose resin, cyclic olefin resin, etc.), and has low birefringence as an optical material. Suitable for applications requiring zero birefringence.
  • the absolute value of the in-plane phase difference Re exceeds 30 nm, it means that the refractive index anisotropy is high, and it cannot be used for applications requiring low birefringence or zero birefringence as an optical material. There is. Moreover, in order to improve the mechanical strength of an optical material (for example, a film, a sheet, etc.), it may be stretched, but when the absolute value of the retardation in the in-plane direction after the stretching process exceeds 30 nm, No low birefringence or zero birefringence material is obtained as an optical material.
  • an optical material for example, a film, a sheet, etc.
  • the absolute value of the thickness direction retardation Rth is preferably 30 nm or less.
  • the retardation Rth is a value obtained by converting a value measured as a film (or a sheet) into a thickness of 100 ⁇ m.
  • the absolute value of the phase difference Rth is more preferably 20 nm or less, further preferably 15 nm or less, and particularly preferably 11 nm or less.
  • the retardation Rth in the thickness direction is an index that correlates with the viewing angle characteristics of a display device incorporating the optical film when an optical material, particularly an optical film is used. More specifically, the smaller the absolute value of the thickness direction retardation Rth, the better the viewing angle characteristics, and the smaller the change in the color tone of the display color depending on the viewing angle and the lower the contrast.
  • the acrylic thermoplastic resin composition according to the present embodiment has a thickness direction retardation Rth when compared with existing resins (for example, PMMA, PC, triacetylcellulose resin, cyclic olefin resin, etc.) as an optical film.
  • existing resins for example, PMMA, PC, triacetylcellulose resin, cyclic olefin resin, etc.
  • the absolute value of is very small.
  • the glass transition temperature Tg of the acrylic thermoplastic resin composition is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and further preferably 135 ° C. or higher.
  • the acrylic thermoplastic resin composition according to this embodiment preferably has a total light transmittance of 85% or more when evaluated as a film-like or sheet-like molded article. 88% or more, more preferably 90% or more. However, the total light transmittance is a value obtained by converting to a thickness of 100 ⁇ m.
  • the refractive index d blend of the acrylic thermoplastic resin composition according to this embodiment is preferably in the range of 1.48 to 1.53.
  • the refractive index d blend is more preferably in the range of 1.48 to 1.51. If the refractive index d blend is within this range, it can be suitably used as a polarizing plate material used in a liquid crystal television.
  • the refractive index of the conventional polarizing plate material for example, the refractive index of polyvinyl alcohol resin is 1.49 to 1.53, the refractive index of triacetyl cellulose resin is 1.49, and the refractive index of cyclic polyolefin resin is 1. 53.
  • the acrylic thermoplastic resin composition according to the present embodiment has a sufficiently small photoelastic coefficient C (approximately zero), and when formed into an optical film, regardless of the presence or absence of stretching.
  • the optical film is characterized by the fact that the absolute values of the in-plane retardation Re and the thickness retardation Rth are both small (approximately zero), and optically perfect that cannot be achieved with conventionally known resins. Isotropic can be realized.
  • the acrylic thermoplastic resin composition according to the present embodiment can simultaneously achieve high heat resistance.
  • the optical film formed by molding the acrylic thermoplastic resin composition according to this embodiment is suitable for applications that do not require birefringence, such as a polarizing plate protective film. Moreover, it is used suitably also for uses, such as a phase difference film, a phase difference plate, a transparent plastic substrate, and a lens.
  • the acrylic thermoplastic resin composition according to the present embodiment is suitably used as an optical material, for example, as a molded body such as an optical film, a display substrate, a lens, a pickup lens, a touch panel, and a transparent plastic substrate used for solar cells. Can be used.
  • an optical communication system, an optical switching system, and an optical measurement system it can be used for waveguides, lenses, lens arrays, optical fibers, optical fiber coating materials, LED lenses, lens covers, and the like.
  • the acrylic thermoplastic resin composition according to the present embodiment is, for example, an extrusion-molded body such as a sheet, film, strand, or pipe, an injection-molded body such as a disk, cube, or plate, and press molding. It can be formed into a body or the like. These molded articles have characteristics according to the characteristics of the acrylic thermoplastic resin composition according to the above-described embodiment.
  • the thickness of the film-shaped or sheet-shaped molded product is preferably 1 to 10,000 ⁇ m, more preferably 1 to 5000 ⁇ m, and further preferably 1 to 3000 ⁇ m.
  • a method for forming the acrylic thermoplastic resin composition according to the present embodiment into a molded body for example, a method such as extrusion molding or solution cast molding can be used for molding into a film-shaped or sheet-shaped molded body. .
  • an acrylic thermoplastic resin composition in extrusion molding, can be melted and formed into a sheet or film using an extruder equipped with a T die, a circular die or the like.
  • various additives and thermoplastic resins other than the acrylic thermoplastic resin composition according to the present embodiment are melt kneaded together with the acrylic thermoplastic resin composition according to the present embodiment to obtain a molded body. You can also.
  • an acrylic thermoplastic resin composition is dissolved in a solvent such as chloroform or methylene dichloride to form a polymer solution, and then cast, dried and solidified to form a sheet or film. .
  • the stretching of the sheet-shaped or film-shaped molded body can be performed continuously by extrusion molding and cast molding.
  • an unstretched film or sheet is longitudinally uniaxially stretched in the mechanical flow direction, transversely uniaxially stretched in a direction perpendicular to the mechanical flow direction, or by simultaneous biaxial stretching method of roll stretching and tenter stretching, and tenter stretching simultaneously.
  • a biaxially stretched film can be obtained by stretching by a biaxial stretching method, a biaxial stretching method by tubular stretching, or the like.
  • the strength of the compact can be improved by stretching.
  • the draw ratio is 0.1% or more and 300% or less in at least one direction, preferably 0.2% or more and 290% or less, and more preferably 0.3% or more and 280% or less. By extending into this range, a molded article having further excellent optical properties such as strength, transparency and birefringence can be obtained.
  • the stretched molded body can be subjected to heat treatment (annealing) for the purpose of stabilizing its mechanical properties and optical properties.
  • the conditions for the heat treatment may be appropriately selected similarly to the conditions for the heat treatment performed on a conventionally known sheet or film, and are not particularly limited.
  • the molded body according to the present embodiment for example, a sheet-like or film-like molded body, can be subjected to surface functionalization treatment such as antireflection treatment, transparent conductive treatment, electromagnetic wave shielding treatment, gas barrier treatment and the like.
  • the injection molded body can be obtained by a conventionally known method in the range of injection molding temperature 200 to 260 ° C., mold temperature 50 to 100 ° C., injection pressure 5 to 20 MPa, holding pressure 1 to 10 MPa. it can.
  • the molded body according to this embodiment includes, for example, a polarizing plate protective film, a quarter-wave plate, and a half-wave plate used in displays such as liquid crystal displays, plasma displays, organic EL displays, field emission displays, and rear projection televisions.
  • displays such as liquid crystal displays, plasma displays, organic EL displays, field emission displays, and rear projection televisions.
  • liquid crystal optical compensation films such as retardation plates, viewing angle control films, display front plates, display substrates, lenses, etc., transparent substrates used in solar cells, transparent conductive substrates such as touch panels, etc. Can do.
  • the molded body according to the present embodiment includes waveguides, lenses, lens arrays, optical fibers, optical fiber coating materials, LED lenses, lens covers, and the like in the fields of optical communication systems, optical switching systems, and optical measurement systems. Can also be used.
  • Tg glass transition temperature
  • the refractive index d A of the first acrylic resin and the refractive index d B of the second acrylic resin are measured using a refractive index measuring apparatus (MODEL 2010 PRISM COUPLER manufactured by Metricon).
  • the refractive index of the press film obtained by the method described later was measured at a measurement wavelength of 633 nm in a room temperature atmosphere.
  • stretched film The press film was stretched uniaxially at a stretching temperature (Tg + 20) ° C. and a stretching speed (500 mm / min) using an Instron 5t tensile tester to form a stretched film.
  • stretched films stretched films having stretch ratios of 100%, 200%, and 300%, respectively, were prepared and subjected to the following characteristic evaluation.
  • (B-3-1) Measurement of birefringence Measurement was performed by a rotating analyzer method using RETS-100 manufactured by Otsuka Electronics.
  • the value of birefringence is a value of light having a wavelength of 550 nm.
  • Birefringence ( ⁇ n) was calculated by the following formula. The obtained value was converted to a film thickness of 100 ⁇ m and used as a measured value.
  • ) of birefringence ( ⁇ n) was determined as follows.
  • ⁇ n nx ⁇ ny
  • the refractive index d blend of the acrylic thermoplastic resin composition was determined by the method described above using a refractive index measuring device (MODEL 2010 PRISM COUPLER manufactured by Metricon). The refractive index was measured at a measurement wavelength of 633 nm in a room temperature atmosphere.
  • Tg glass transition temperature
  • the raw material solution was introduced from the raw material solution introduction nozzle into the glass reactor by pressure feeding.
  • the initiator solution was introduced from the initiator solution introduction nozzle with a syringe to start the polymerization reaction. After 3 hours from the start of the reaction, the reaction was terminated, and the polymer solution was recovered.
  • the obtained polymer solution and methanol as a poor solvent were simultaneously supplied to a homogenizer, and emulsified, dispersed and extracted.
  • the separated and precipitated polymer was collected and dried at 130 ° C. for 2 hours under vacuum to obtain the desired first acrylic resin (A-1).
  • the obtained first acrylic resin (A-1) was subjected to structural unit analysis, glass transition temperature measurement, and molecular weight measurement by the above methods.
  • the results were as follows.
  • a structural unit derived from methyl methacrylate is represented as “MMA”
  • a structural unit derived from N-phenylmaleimide is represented as “N-PheMI”.
  • Structural unit: MMA / N-PheMI 97/3 (mass%)
  • Mw 20.4 ⁇ 10 4
  • Mw / Mn 1.71 Tg: 124 ° C
  • Table 1 shows the composition (ratio of structural units) and heat resistance of the acrylic resin obtained as described above. Moreover, each acrylic resin was shape
  • the weather resistance is based on the weather resistance (yellow index) of the acrylic resin (C-1), with the yellow index larger than that being "B” and the smaller one being "A”. . The smaller the yellow index, the less yellow and preferable.
  • the absolute value of the photoelastic coefficient C is larger than 3.0 ⁇ 10 ⁇ 12 Pa ⁇ 1 when the acrylic resin obtained in Synthesis Examples 1 to 13 is used as a molded body alone. It can be seen that the absolute value of the in-plane retardation Re is larger than 30 nm and the low birefringence is not sufficient.
  • Examples 1 to 15 The first acrylic resin and the second acrylic resin were dissolved in tetrahydrofuran (THF), respectively, and then stirred and mixed so that the blend ratios shown in Tables 2 and 3 were obtained.
  • THF tetrahydrofuran
  • the obtained THF mixed solution was dropped into methanol as a poor solvent so that the methanol / THF ratio was in the range of 3 to 10 to obtain a desired acrylic thermoplastic resin composition.
  • Table 2 shows the composition (ratio of structural units) and heat resistance of the obtained acrylic thermoplastic resin composition. Furthermore, each acrylic thermoplastic resin composition was molded as a press film according to the above-described method. Then, a 100% stretched film was molded from the press film according to the method described above, and its optical characteristics were evaluated. The characteristic evaluation results are shown in Table 2.
  • FIG. 1 is a diagram showing a 1 H-NMR spectrum of the acrylic thermoplastic resin composition obtained in Example 3.
  • FIG. 1 is a diagram showing a 1 H-NMR spectrum of the acrylic thermoplastic resin composition obtained in Example 3.
  • the acrylic thermoplastic resin composition of the present invention had excellent compatibility and good transparency.
  • the optical film obtained from the acrylic thermoplastic resin composition of the present invention has very small absolute values of retardation and photoelastic coefficient, which are optical characteristics.
  • the optical films of Examples 2 to 9, 14 and 15 exhibit so-called zero-zero birefringence.
  • the optical film made of the acrylic resin (C-1) as a comparative example was inferior in optical characteristics in that the absolute value of the photoelastic coefficient was large and the absolute value of the phase difference was large.
  • the acrylic thermoplastic resin compositions obtained in Examples 1 to 15 had high heat resistance, good weather resistance, and low water absorption.
  • Example 6 From a comparison between Example 6 and Examples 1, 5, 7, and 9, when the difference in weight average molecular weight between the first acrylic resin and the second acrylic resin is 10,000 or more, the melt flow rate is large. It can be seen that the moldability is improved to such an extent that almost no streaks are observed in the appearance of the molded product. Further, from Examples 11 and 12, when the weight average molecular weight of the acrylic resin having a high glass transition temperature is large or when there is almost no difference in the weight average molecular weight, the molding process is possible, but the processability is It turns out that it is low compared with other examples.
  • Example 16 From the press film obtained by the same method as in Example 3, 100%, 200% and 300% stretched films were molded according to the method described above, and the optical properties were evaluated. The evaluation results are shown in Table 5.
  • Comparative Example 2 From the press film obtained in the same manner as in Comparative Example 1, 100%, 200% and 300% stretched films were molded according to the method described above, and the optical properties were evaluated. The evaluation results are shown in Table 5.
  • FIG. 2A is a schematic view showing the three-stage plate produced in Example 17.
  • the three-stage plate 10 includes a first plate part 1 having a thickness of 1 mm, a second plate part 2 having a thickness of 1 mm, and a third plate part 3 having a thickness of 3 mm.
  • the molding conditions for the three-stage plate were as follows. Cylinder temperature was set to 230 degreeC, 240 degreeC, 240 degreeC, and 240 degreeC from the hopper side. The mold temperature was set at 80 ° C., the injection time was 10 seconds, and the cooling time was 30 seconds. The molten resin was filled by applying a pressure 5 MPa higher than the injection pressure at which the resin just fills the mold.
  • the optical characteristics of the obtained three-stage plate were evaluated, and it was confirmed that the retardation (Re) in the plate was less than 15 nm in the entire region.
  • the three-stage plate was evaluated by a crossed Nicol test in which a test piece was placed between two orthogonal polarizing plates and whether transmitted light (the presence or absence of light leakage) was observed.
  • Comparative Example 3 a three-stage plate obtained by injection molding in the same manner as in Example 17 above using the acrylic thermoplastic resin obtained in Comparative Example 1 was evaluated.
  • FIGS. 2B and 2C are diagrams showing the results of the crossed Nicols test of Example 17 and Comparative Example 3, respectively.
  • the acrylic thermoplastic resin according to the present invention is a material suitable for injection molded articles such as lenses, pickup lenses, and lens arrays that require low birefringence and optical uniformity.
  • the optical film made of the acrylic thermoplastic resin composition of the present invention has excellent heat resistance and high optical isotropy (very small birefringence value, very small photoelastic coefficient) that cannot be achieved with existing resins. It is confirmed that it has. In addition, it can be confirmed that the amount of change in birefringence when the film is formed or subjected to an arbitrary stretching process to increase the film strength is extremely small.
  • This feature does not cause (orientation) birefringence due to the orientation of polymer chains due to the flow during melt molding during molding or stretching, and (photoelastic) birefringence due to residual stress or external force during molding Is extremely advantageous for industrial application in that These characteristics are suitable for polarizing plate protective film applications.
  • the acrylic thermoplastic resin composition of the present invention is excellent in transparency, heat resistance, weather resistance, and birefringence is highly controlled.
  • Polarizing plate protective films used for displays such as liquid crystal displays, plasma displays, organic EL displays, field emission displays, rear projection televisions, retardation plates such as quarter-wave plates and half-wave plates, viewing angle control films, etc.
  • the liquid crystal optical compensation film, display front plate, display substrate, lens and the like, and transparent substrates used for solar cells, transparent conductive substrates such as touch panels, and the like can be suitably used.
  • the acrylic thermoplastic resin composition of the present invention is used in the fields of optical communication systems, optical switching systems, and optical measurement systems, such as waveguides, lenses, lens arrays, optical fibers, optical fiber coating materials, LED lenses, It can also be used for lens covers.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
PCT/JP2012/066550 2011-07-01 2012-06-28 アクリル系熱可塑性樹脂組成物及びその成形体 WO2013005634A1 (ja)

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IN2445MUN2013 IN2013MN02445A (zh) 2011-07-01 2012-06-28
JP2012549194A JP5190564B2 (ja) 2011-07-01 2012-06-28 アクリル系熱可塑性樹脂組成物及びその成形体
EP12807338.4A EP2727961B8 (en) 2011-07-01 2012-06-28 Acrylic thermoplastic resin composition and molded article thereof
CN201280030159.7A CN103619946B (zh) 2011-07-01 2012-06-28 丙烯酸系热塑性树脂组合物及其成型体
KR1020137033322A KR101536505B1 (ko) 2011-07-01 2012-06-28 아크릴계 열가소성 수지 조성물 및 그 성형체
US14/129,230 US10030134B2 (en) 2011-07-01 2012-06-28 Acrylic thermoplastic resin composition and molded article thereof
US15/298,786 US20170037236A1 (en) 2011-07-01 2016-10-20 Acrylic Thermoplastic Resin Composition and Molded Article Thereof
US16/029,494 US20180312682A1 (en) 2011-07-01 2018-07-06 Optical Material

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JP2011147330 2011-07-01

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US15/298,786 Continuation US20170037236A1 (en) 2011-07-01 2016-10-20 Acrylic Thermoplastic Resin Composition and Molded Article Thereof
US16/029,494 Continuation US20180312682A1 (en) 2011-07-01 2018-07-06 Optical Material

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015110757A (ja) * 2013-10-31 2015-06-18 住友化学株式会社 （メタ）アクリル系樹脂組成物及びそれを用いた（メタ）アクリル系樹脂フィルム
JP2016017128A (ja) * 2014-07-08 2016-02-01 株式会社日本触媒 樹脂組成物、該樹脂組成物を含むフィルム、並びに該フィルムを用いた偏光子保護フィルム、偏光板及び画像表示装置
JP2017101225A (ja) * 2015-11-20 2017-06-08 旭化成株式会社 メタクリル系樹脂、メタクリル系樹脂組成物、フィルム、製造方法
JP2017179355A (ja) * 2016-03-29 2017-10-05 旭化成株式会社 メタクリル系樹脂組成物、及び成形体
JP2017186509A (ja) * 2016-03-31 2017-10-12 旭化成株式会社 メタクリル系樹脂組成物
JP2018002994A (ja) * 2016-06-22 2018-01-11 旭化成株式会社 メタクリル系樹脂組成物、光学フィルム、光学部品
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CN112300325B (zh) * 2020-11-09 2021-09-07 聚纶材料科技（深圳）有限公司 光学薄膜及其制造方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55102614A (en) 1979-01-29 1980-08-06 Asahi Chem Ind Co Ltd Styrene copolymer and its preparation
JPS57153008A (en) 1981-03-19 1982-09-21 Asahi Chem Ind Co Ltd Methacrylic resin having excellent heat resistance
JPS61171708A (ja) 1984-12-14 1986-08-02 Mitsubishi Rayon Co Ltd 耐熱性樹脂、その製造法およびそれからなる光学用素子
JPS61252211A (ja) 1985-05-01 1986-11-10 Asahi Chem Ind Co Ltd 光学純度の良い耐熱性アクリル樹脂の製造法
JPS62270648A (ja) 1986-05-19 1987-11-25 Mitsubishi Rayon Co Ltd 耐熱性メタクリル樹脂組成物
JPS6479248A (en) 1987-09-22 1989-03-24 Denki Kagaku Kogyo Kk Transparent heat-resistant resin composition
JPH0586252A (ja) 1992-04-03 1993-04-06 Nippon Shokubai Co Ltd 熱可塑性樹脂組成物
JPH06242301A (ja) 1993-02-16 1994-09-02 Kuraray Co Ltd 光学素子
JPH09255838A (ja) 1996-03-25 1997-09-30 Nippon Shokubai Co Ltd 熱可塑性樹脂組成物

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6195011A (ja) * 1984-10-17 1986-05-13 Toray Ind Inc 光デイスク基板
JPS6210157A (ja) * 1985-07-08 1987-01-19 Mitsubishi Rayon Co Ltd 耐熱性メタクリル樹脂組成物
US4810055A (en) * 1986-10-02 1989-03-07 Toray Industries, Inc. Heat resisting plastic optical fiber and method for its manufacture
US5155190A (en) * 1988-09-06 1992-10-13 Hitachi Chemical Company Process for producing poly methyl methacrylate/N-substituted maleimide optical resin
US5073615A (en) * 1989-03-13 1991-12-17 Continental Polymers, Inc. High temperature heat resistant acrylics
JP4424636B2 (ja) * 2000-04-11 2010-03-03 株式会社日本触媒 透明耐熱性熱可塑性樹脂組成物
JP2002187993A (ja) * 2000-12-21 2002-07-05 Hitachi Chem Co Ltd 非複屈折性光学用樹脂組成物及びこれを用いた光学用素子
CN101180359A (zh) * 2005-05-30 2008-05-14 株式会社钟化 树脂组合物
WO2009031544A1 (ja) * 2007-09-04 2009-03-12 Denki Kagaku Kogyo Kabushiki Kaisha 熱可塑性共重合樹脂及びその光学成形体
KR101201168B1 (ko) * 2007-12-27 2012-11-13 아사히 가세이 케미칼즈 가부시키가이샤 아크릴계 열가소성 수지, 및 광학 재료용 성형체
KR20090076753A (ko) * 2008-01-08 2009-07-13 주식회사 엘지화학 투명한 수지 조성물
KR101091534B1 (ko) * 2008-04-30 2011-12-13 주식회사 엘지화학 광학 필름 및 이를 포함하는 정보전자 장치
JP5283701B2 (ja) * 2008-07-31 2013-09-04 旭化成ケミカルズ株式会社 アクリル系熱可塑性樹脂、及びその成形体
KR101091537B1 (ko) * 2009-01-06 2011-12-13 주식회사 엘지화학 광학 필름 및 이를 포함하는 액정 표시 장치
US8536275B2 (en) * 2010-06-30 2013-09-17 Lg Chem, Ltd. Acryl-based copolymers and optical film including the same
US10030134B2 (en) * 2011-07-01 2018-07-24 Asahi Kasei Kabushiki Kaisha Acrylic thermoplastic resin composition and molded article thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55102614A (en) 1979-01-29 1980-08-06 Asahi Chem Ind Co Ltd Styrene copolymer and its preparation
JPS57153008A (en) 1981-03-19 1982-09-21 Asahi Chem Ind Co Ltd Methacrylic resin having excellent heat resistance
JPS631964B2 (zh) 1981-03-19 1988-01-14 Asahi Chemical Ind
JPS61171708A (ja) 1984-12-14 1986-08-02 Mitsubishi Rayon Co Ltd 耐熱性樹脂、その製造法およびそれからなる光学用素子
JPS61252211A (ja) 1985-05-01 1986-11-10 Asahi Chem Ind Co Ltd 光学純度の良い耐熱性アクリル樹脂の製造法
JPS62270648A (ja) 1986-05-19 1987-11-25 Mitsubishi Rayon Co Ltd 耐熱性メタクリル樹脂組成物
JPS6479248A (en) 1987-09-22 1989-03-24 Denki Kagaku Kogyo Kk Transparent heat-resistant resin composition
JPH0586252A (ja) 1992-04-03 1993-04-06 Nippon Shokubai Co Ltd 熱可塑性樹脂組成物
JPH06242301A (ja) 1993-02-16 1994-09-02 Kuraray Co Ltd 光学素子
JPH09255838A (ja) 1996-03-25 1997-09-30 Nippon Shokubai Co Ltd 熱可塑性樹脂組成物

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
"Chemical Review", 1988, JAPAN SCIENTIFIC SOCIETIES PRESS
"Chemical Review", 1998, JAPAN SCIENTIFIC SOCIETIES PRESS
MACROMOLECULES, vol. 39, 2006, pages 3019 - 3023
MONTHLY DISPLAY, April 2005 (2005-04-01)
POLYMER ENGINEERING AND SCIENCE, vol. 39, 1999, pages 2349 - 2357
See also references of EP2727961A4
SEIKEI-KAKOU, vol. 21, no. 7, 2009, pages 426

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JP2015110757A (ja) * 2013-10-31 2015-06-18 住友化学株式会社 （メタ）アクリル系樹脂組成物及びそれを用いた（メタ）アクリル系樹脂フィルム
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EP2727961A4 (en) 2014-12-31
CN103619946B (zh) 2016-08-17
IN2013MN02445A (zh) 2015-06-12
US10030134B2 (en) 2018-07-24
EP2727961B8 (en) 2016-10-19
EP2727961A1 (en) 2014-05-07
TWI468456B (zh) 2015-01-11
JP5190564B2 (ja) 2013-04-24
KR101536505B1 (ko) 2015-07-13
US20180312682A1 (en) 2018-11-01
US20140128547A1 (en) 2014-05-08
KR20140013081A (ko) 2014-02-04
CN103619946A (zh) 2014-03-05
TW201302899A (zh) 2013-01-16
US20170037236A1 (en) 2017-02-09
JPWO2013005634A1 (ja) 2015-02-23

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